Ilya Pobelov

From Redox Gating to Quantized Charging

Electron transport characteristics were studied in redox molecule-modified tunneling junctions Au(111)/6-thiohexanoylferrocene (Fc6)/solution gap/Au STM tip in the absence and in the presence of gold nanoclusters employing an electrochemical STM setup. We observed transistor- and diode-like current-voltage responses accounted for by the redox process at the ferrocene moiety. We demonstrate that the reorganization energy of the redox site decreases with decreasing gap size. As a unique new feature, we discovered the formation of uniform (size approximately 2.4 nm) gold nanoparticles, upon multiple oxidation/reduction cycles of the Fc6 adlayer. The immobilized nanoparticles modify the electron transport response of the Fc6 tunneling junctions dramatically. On top of embedded single nanoparticles we observed single-electron Coulomb charging signatures with up to seven narrow and equally spaced energy states upon electrochemical gating. Our results demonstrate the power of the electrochemical approach in molecular electronics and offer a new perspective toward two-state and multistate electronic switching in condensed media at room temperature.

Current measurements in a wide dynamic range—applications in electrochemical nanotechnology

Current measurements in a wide dynamic range from low picoamperes up to a few milliamperes are usually carried by implementing logarithmic current-to-voltage converter circuits. Conductance studies in nanoscale metal | molecule | metal junctions require measurements with a high dynamic range, good accuracy and reasonable speed simultaneously. In this work we propose two novel circuit solutions which comply with these conditions: one is based on a high-accuracy, fine-tunable logarithmic current-to-voltage converter. Another circuit implements a double-output (or multiple-output) linear current-to-voltage converter, for which the problem of range-switching has been circumvented. Both circuits were applied in constructing a low-current bipotentiostat dedicated to the electrochemical formation of molecular-scale gaps, and a novel scanning tunnelling microscope preamplifier stage for current-distance spectroscopy studies.

Fabrication of cone-shaped boron doped diamond and gold nanoelectrodes for AFM?SECM

We demonstrate a reliable microfabrication process for a combined atomic force microscopy (AFM) and scanning electrochemical microscopy (SECM) measurement tool. Integrated cone-shaped sensors with boron doped diamond (BDD) or gold (Au) electrodes were fabricated from commercially available AFM probes. The sensor formation process is based on mature semiconductor processing techniques, including focused ion beam (FIB) machining, and highly selective reactive ion etching (RIE). The fabrication approach preserves the geometry of the original AFM tips resulting in well reproducible nanoscaled sensors. The feasibility and functionality of the fully featured tips are demonstrated by cyclic voltammetry, showing good agreement between the measured and calculated currents of the cone-shaped AFM-SECM electrodes.

An approach to measure electromechanical properties of atomic and molecular junctions

We describe a new setup for simultaneous measurements of force and current in conductive nanocontacts in a liquid environment with a high sampling rate and resolution. A lab-built current-to-voltage converter allows measurements of the current over seven orders of magnitude. As examples, we studied conductances and mechanical forces upon formation and breaking of gold atomic contacts and of two molecular junctions containing 1,2-di(4-pyridyl)ethyne (M1) and 1,4-di(4-pyridyl)buta-1,3-diyne (M2). We found that the forces required to deform or break gold atomic contacts depend critically on the surrounding medium. Further, they show non-linear behaviour in dependence of the number N of gold atoms detached. The electromechanical properties of the two types of molecular junctions upon stretching were analysed by correlating breaking forces with simultaneously measured junction conductances. A rather complex behaviour in a wide range of forces was discovered. Comparison of the current-probe atomic force microscopy experiments on the rupture of molecular junctions with STM-based break junction experiments enables the assignment of breaking forces of molecular junctions to the corresponding junction conductances.

Correlation of breaking forces, conductances and geometries of molecular junctions

Electrical and mechanical properties of elongated gold-molecule-gold junctions formed by tolane-type molecules with different anchoring groups (pyridyl, thiol, amine, nitrile and dihydrobenzothiophene) were studied in current-sensing force spectroscopy experiments and density functional simulations. Correlations between forces, conductances and junction geometries demonstrate that aromatic tolanes bind between electrodes as single molecules or as weakly-conductive dimers held by mechanically-weak π − π stacking. In contrast with the other anchors that form only S-Au or N-Au bonds, the pyridyl ring also forms a highly-conductive cofacial link to the gold surface. Binding of multiple molecules creates junctions with higher conductances and mechanical strengths than the single-molecule ones.

Electrochemical current-sensing atomic force microscopy in conductive solutions

Insulated atomic force microscopy probes carrying gold conductive tips were fabricated and employed as bifunctional force and current sensors in electrolyte solutions under electrochemical potential control. The application of the probes for current-sensing imaging, force and current-distance spectroscopy as well as scanning electrochemical microscopy experiments was demonstrated.

Atomic force microscopy-scanning electrochemical microscopy: influence of tip geometry and insulation defects on diffusion controlled currents at conical electrodes.

Numerical simulations were performed to predict the amperometric response of conical electrodes used as atomic force microscopy-scanning electrochemical microscopy (AFM-SECM) probes. A simple general expression was derived which predicts their steady state limiting current as a function of their insulation sheath thickness and cone aspect ratio. Simulated currents were successfully compared with experimental currents. Geometrical parameters such as insulation angle and tip bluntness were then studied to determine their effect on the limiting current. Typical tip defects were also modeled using 3D simulations, and their influence on the current was quantified. Although obtained for SECM-AFM probes, these results are directly applicable to conical micro- and nanoelectrodes.

Reduction of an Ensemble of Platinum(II) Aquachloride Complexes: Dynamic Effect of the Solvent

Dynamic effect of the solvent is studied for the first time ever for the process that occurs in the vicinity of the activationless region, namely, the reaction of electroreduction of an ensemble of platinum(II) aquachloride complexes on a negatively charged mercury electrode. A sequential analysis of the sucrose influence on the interface structure and the equilibrium solvation energy is performed. Estimates of the above effects are given. These are necessary for subtracting the dependence of the electron transfer rate on the solvent relaxation time from the observed overall dependence on the concentration of the viscosity-forming additive. A procedure for estimating the sucrose concentration in the reaction layer is suggested and on this basis the increase in the local viscosity near the interface, which is caused by the presence of a surface excess of sucrose, is approximately taken into account. The potential interval where the reaction under study occurs in an almost adiabatic mode is determined.

Dynamic breaking of a single gold bond

While one might assume that the force to break a chemical bond gives a measure of the bond strength, this intuition is misleading. If the force is loaded slowly, thermal fluctuations may break the bond before it is maximally stretched, and the breaking force will be less than the bond can sustain. Conversely, if the force is loaded rapidly it is more likely that the maximum breaking force is measured. Paradoxically, no clear differences in breaking force were observed in experiments on gold nanowires, despite being conducted under very different conditions. Here we explore the breaking behaviour of a single Au–Au bond and show that the breaking force is dependent on the loading rate. We probe the temperature and structural dependencies of breaking and suggest that the paradox can be explained by fast breaking of atomic wires and slow breaking of point contacts giving very similar breaking forces.

Reduction of an Ensemble of Chloride Aquacomplexes of Platinum(II): An Analysis in the Framework of Phenomenological Approach

A general approach is offered to a phenomenological analysis of experimental data on the kinetics of an electrode reaction complicated by chemical stages. The approach is based on a consideration of the way the process rate depends on the supporting-electrolyte concentration at a constant electrode charge. The possibilities of the approach are illustrated by the example of the reduction of chloride complexes of Pt(II) in the presence of chloride, indifferent (in the sense of inner-sphere substitution), and mixed supporting electrolytes. The performed analysis generalizes the Frumkin–Petrii relationship, which determines the average charge of the single reactant in the solution bulk. A system may contain an ensemble of reactants. In this case, in addition to the bulk properties of the system, similar relationships take into account the interface structure and the balance between partial rate constants for parallel reactions involving reactants of different chargeness.